JPH10110381A - Deodorizing knitted fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a knitted fabric excellent in durability and comprising acrylic synthetic fiber having high deodorizing performance against various offensive odors emitted in daily life, and to provide a method for producing the knitted fabric. SOLUTION: This knitted fabric comprises acrylic synthetic fiber composed of a copolymer A with acrylonitrile as the main constituent unit and 1-40wt.% of a polymer B miscible with the copolymer A but incompatible therewith. In this case, the polymer B is in a phase-separated state, containing 0.5-20wt.% fine powder with a metal silicate or metal aluminosilicate 0.5-10Lμm in average particle size as active ingredient and also bearing 0.1-20wt.% of an amino compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in durability and is good against various malodors such as ammonia, amines, hydrogen sulfide, mercaptans, acetic acid and aldehydes, which are typical malodors generated in daily life. The present invention relates to a knitted fabric containing an acrylic synthetic fiber having excellent deodorizing performance and a method for producing the same.

[0002]

2. Description of the Related Art Knitted fabrics are mainly used in the fields of clothing, bedding, interiors, and industrial materials. Clothing and bedding include clothes, underwear, underwear, socks, and the like. Covers such as futons and pillows, sheets, blankets, etc .; interiors such as curtains, mats, carpets, carpet covers, and upholstery; and industrial materials such as vehicles, interior materials such as shoes and cases, and buildings. It is used as an interior material used for inner walls and the like, as a lining material for building materials and other furniture furniture, as a surface material, as an interior material for vehicles, and the like. With respect to imparting deodorant properties to these knitted fabrics, in recent years, interest in comfort in a living environment has been increasing, and proposals have been made regarding removal of offensive odors in various environments such as indoors and vehicles. In imparting deodorizing performance to these knitted fabrics, a method of mixing fibers imparted with deodorizing performance in a process of producing a knitted fabric, processing of a deodorant agent into a knitted fabric, and the like can be mentioned.

[0003] As a method of imparting a function of eliminating odors, which has been regarded as a problem as a bad odor, to fibers and textile products, there is a method of grafting a vinyl monomer having an acidic group onto fibers (Japanese Patent Publication No. 3-77308, 2-583
No. 92, Japanese Unexamined Patent Publication No. Sho 62-142562),
Copper compounds (JP-A-61-231202, JP-A-6-231202)
2-6978) and various deodorants (JP-A-61-2).
58076, JP-A-56-100060)
There is known a method of adhering to the fiber surface. Also,
As a method of introducing a vinyl monomer having a deodorizing function into a fiber, a method of copolymerizing a vinyl monomer having an acidic group and fibrillating the polymer may be mentioned.

[0004] Among these methods, however, the grafting involves changes in the texture of the fibers and textile products, the inability to obtain a uniform reaction efficiency and the inability to sufficiently exert the deodorizing effect, and the similarity to the dyeing process. In this case, the graft reaction must be performed, which causes problems such as an increase in the number of steps, and contamination of the processing machine and wastewater by the processing liquid at that time. In addition, if it is a vinyl monomer having an acidic group, it is often effective only for basic malodor, and it is hard to say that it has sufficient deodorizing performance.

[0005] In the post-processing of adhering the fine powder having a deodorizing effect to the fiber surface and the post-processing of dipping, applying and spraying a solution having a deodorizing effect on the fiber product, the unique texture of the fiber and the texture of the product are obtained. There are drawbacks such as a drop, and a drop in the agent due to washing with water, washing at home or dry cleaning, and insufficient washing durability.

As a method of introducing a vinyl monomer having a deodorizing function into fibers, there is a method of copolymerizing a vinyl monomer having an acidic group at the time of polymerization to produce a fiber of the polymer. Since there are more vinyl monomers having an acidic group having an odor effect inside the fiber than on the fiber surface, the rate of direct contact with malodor is small compared to the introduction rate of the vinyl monomer having an acidic group, and the deodorizing effect is poor. There are drawbacks such as sufficientness, deterioration of fiber properties, and deterioration of hand. Furthermore, because it is a vinyl monomer having an acidic group,
The effect is the same as that at the time of the grafting described above, and it is difficult to say that the deodorizing performance is sufficient.

[0007] In recent years, bad smells caused by smoking in indoor environments have been regarded as a problem due to an increase in non-smokers and smokers, and an increase in smoking rights. In most cases, the odor component in these living environments is not a single component but a mixture of a plurality of compounds including an acidic component, a basic component, and a neutral component. The odor caused by smoking is a mixture of thousands to tens of thousands of compounds.The main components of the odor can be divided into basic components such as ammonia and nicotine, acidic components such as acetic acid and aldehyde, and neutral components. It is said. Above all, deodorization of a part of basic odor and acidic odor is performed by the above-mentioned method and the like, but is not sufficient. Almost no aldehydes have sufficient deodorizing performance and durability. Regarding the aldehyde deodorizing method, activated carbon is adjusted to pH 7 or more (JP-A-54-74268), spinel type Activated carbon compositions containing the above-mentioned metal oxides (Japanese Patent Application Laid-Open No. 48-38291) are known, but they have problems in the effects at normal temperature, durability, processing methods, costs, and the like. As a method for eliminating odor using an amino compound, a deodorant polymer using polyalkyleneimine (Japanese Patent Application Laid-Open No. 3-218766) is known. It has drawbacks such as ineffectiveness in washing durability and basic odor.
As a method for eliminating both the acidic odor and the basic odor, a fiber product obtained from a spun yarn obtained by mixing a fiber containing an acidic group and a fiber obtained by processing an amino compound (Japanese Patent Application Laid-Open No. 8-74131). Publication), but it is not a method of deodorizing acidic and basic malodors with a single fiber, but a method obtained by blending fibers having deodorizing performance against each malodor. However, it cannot be said that the original deodorant performance, washing durability, and dyeing durability are at a sufficiently satisfactory level. There is also a method of fixing deodorant components to textiles using a resin or the like in order to prevent the deodorant components from falling off due to washing or dry cleaning, but there are drawbacks such as complicated processing steps and changes in fiber texture. In addition, it is not at a sufficiently satisfactory level because it has drawbacks such as a decrease in deodorant performance due to coating with a deodorant component.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to contain a deodorant acrylic synthetic fiber which has washing resistance, has an excellent deodorizing effect, and maintains the original performance and texture of a knitted fabric. And a method of manufacturing the same.

[0009]

The gist of the present invention is to provide a copolymer (A) having acrylonitrile as a main constituent unit, and a copolymer (A) which is miscible and incompatible with the copolymer (A). In the acrylic synthetic fiber comprising 1 to 20% by weight of the polymer (B), the polymer (B) exists in a phase-separated state, and the metal silicate salt having an average particle size of 0.5 to 10 μm or An amino compound is added to a knitted fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight of a fine powder containing aluminosilicate metal salt as an active ingredient.
An object of the present invention is to provide a deodorant knitted fabric characterized in that the woven fabric adheres to an amount of up to 20% by weight and a method for producing the same.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The copolymer (A) containing acrylonitrile as a main constituent unit used in the present invention comprises an acrylonitrile copolymer containing at least 40% by weight of acrylonitrile, and contains any other copolymerizable monomer. It can be used together. For example, methyl acrylate, alkyl acrylates such as ethyl acrylate, methyl methacrylate, alkyl methacrylate such as ethyl methacrylate, styrene, vinyl acetate, vinyl chloride,
Neutral monomers such as vinylidene chloride, vinyl ethyl ether, and methacrylonitrile; and acidic acids such as acrylic acid, methacrylic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, and 2-acrylamide-2-methylpropanesulfonic acid. Those obtained by copolymerizing a monomer and an appropriate combination of an ammonium salt and an alkali metal salt of the monomer at a ratio of 60% by weight or less are exemplified. The acrylic copolymer may be produced by any method such as suspension polymerization, solution polymerization, emulsion polymerization and the like.

It is essential that the polymer (B) used in the present invention is miscible and incompatible with the polymer (A). Being miscible means that the polymers are
The property that the polymer solutions can be mixed well without agglomeration or gelation, and the incompatibility means that when the solution of the copolymer (A) and the solution of the polymer (B) are mixed, Phase separation without dissolving, or solvent removal, phase separation of copolymer (A) and polymer (B) during molding, or mixing of copolymer (A) and polymer (B) It means that after melt-kneading, they are not uniformly blended with each other but are phase-separated. In general, the phase separation state is preferably such that the polymer (B) is spherical or spheroidal, more preferably spherical having a more uniform size. Although it is possible to use two or more polymers as the polymer (B), it is necessary that the polymer (B) be miscible and incompatible with the polymer (A). Confirmation of phase separation when the solution of the copolymer (A) and the solution of the polymer (B) are mixed,
It can be carried out by a general method, for example, a phase-contrast optical microscope or the like, as long as phase separation is performed in a solution state.

The polymer (B) is not particularly limited as long as it is miscible with the copolymer (A) and is incompatible with the copolymer (A).
Cellulose derivatives such as acetyl cellulose, acetyl propionyl cellulose, acetyl butyl cellulose,
Polyvinyl acetal such as polyvinyl formal, polyvinyl butyral, polyvinyl alcohol derivatives such as cyanoethylated polyvinyl alcohol, polyvinyl acetate,
Vinyl acetate copolymers such as vinyl acetate-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinyl chloride polymers such as acrylonitrile copolymers, polystyrene, styrene polymers such as acrylonitrile-butadiene-styrene copolymers, polymethyl methacrylate, copolymers containing methyl methacrylate as a main component, and the like. Cellulose derivatives or polyvinyl alcohol derivatives are preferred.

In the present invention, the polymer (B) is contained in an amount of 1 to 20% by weight, preferably 2 to 15% by weight, based on the copolymer (A). If the amount of the polymer (B) is less than 1% by weight, a good phase separation state cannot be obtained, and if it exceeds 20% by weight, the fiber performance deteriorates, and it is difficult to produce easily and inexpensively industrially. Become.

As the fine powder used in the present invention, SiO ₂ : 5 to 80 mol% MO _{n / 2} : 5 to 65 mol% Al ₂ O ₃ : 0 to 60 mol in terms of a three-component composition ratio expressed as an oxide. % (M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, magnesium or zirconium, and n represents the valency of the metal) Alternatively, a metal aluminosilicate is used as an active ingredient. Such metal salts are
The crystals have both properties of solid acid and solid base, and exist independently on the surface of one solid particle without neutralizing each other, forming an amphoteric adsorption surface. It has an excellent deodorizing effect due to chemical adsorption to acidic malodors, and has a large specific surface area, excellent contact efficiency with malodors, and also has a physical adsorption function, so it can be effectively deodorized. . When M of the metal MO _{n / 2} , which is one component in the fine powder, is zinc, copper, or silver, it exhibits antibacterial properties. If antibacterial properties are important, use the corresponding fine powder. I just need.

The average particle size of the fine powder containing the metal silicate or the metal aluminosilicate used in the present invention as an active ingredient depends on the particle size distribution, but is preferably 0.1 to 10 μm, and more preferably 1 to 10 μm.
７7 μm. If the average particle size of the fine powder is less than 0.1 μm, agglomeration is likely to occur, and uniform dispersion is difficult unless a special dispersing device or dispersant is used. If it exceeds 10 μm, the filtration pressure increases during spinning and the yarn breaks. Etc. occur, which is not preferable in operation.

The fine powder containing a metal silicate or aluminosilicate used as an active ingredient in the present invention has a BET specific surface area of 100 m ² / g or more, preferably 150 m ² / g or more. This BET specific surface area is 100
If it is lower than m ² / g, the efficiency of contact with malodor decreases, and the deodorizing ability cannot be sufficiently exhibited.

The amount of the fine powder containing the metal silicate or metal aluminosilicate used as an active ingredient in the present invention is 0.5 to 20 with respect to the acrylonitrile copolymer.
%, Preferably 1 to 15% by weight. If the content of the fine powder is less than 0.5% by weight, sufficient deodorizing performance cannot be provided, and if it exceeds 20% by weight, spinnability, fiber quality and spinnability in spinning are undesirably reduced.

In the fiber of the present invention, the fine powder is localized in the phase-separated polymer (B), whereby the deodorizing effect is remarkably improved. Although the reason is not clear, the macrovoids formed by the phase-separated polymer (B) partially have pores opened on the surface communicating with the internal pores, and the malodorous substance is contained in the acrylic fiber. It is considered that the deodorizing effect is improved by making it easier to enter and increasing the contact area with the fine powder. This localization can be confirmed in the same manner as the method for confirming the phase separation. Further, it is considered that the obtained pores can be easily provided to the inside when the amino compound is contained, and the amino compound retained in the fine pores further improves the durability to washing and the like. Further, the amino compound held inside the pores increases the contact area with the malodor as in the case of the fine powder, and improves the deodorizing effect.

As the solvent used in the present invention, any solvent may be used as long as it can dissolve the acrylonitrile copolymer. For example, organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone and the like can be mentioned, which are preferable in terms of solubility, solvent recovery and handling.

In the present invention, the concentration of the solution of the polymer (B) in the organic solvent is 5 to 40% by weight, preferably 10 to 30% by weight. If this concentration is less than 5% by weight, the concentration of the spinning dope decreases, the spinnability decreases, and the fiber properties decrease. On the other hand, when the content exceeds 40% by weight, not only is it difficult to uniformly disperse the fine powder due to an increase in viscosity, but also the spinnability is reduced, and it becomes difficult to produce easily in an industrial manner.

In the present invention, the dispersion concentration of the organic solvent in the fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient is 5 to 40% by weight, preferably 10 to 35% by weight. If the concentration is less than 5% by weight, the concentration of the spinning dope decreases, and the spinnability decreases and the fiber properties decrease. On the other hand, if the content exceeds 40% by weight, a good dispersion state cannot be obtained, and it is difficult to produce easily industrially.

A method of adding a polymer (B) and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient to the acrylonitrile copolymer (A) and mixing them to obtain a stock solution for spinning is described below. A dispersion in which the polymer (B) and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient are dispersed in an organic solvent is added to a solution obtained by dissolving the compound (A) in an organic solvent, and the dispersion is added immediately before spinning and mixed. Just do it. The polymer (B) used in the present invention and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient are dispersed in an organic solvent,
The dissolving method and the method of adding and mixing the prepared solution to the spinning solution containing the acrylonitrile copolymer can be sufficiently mixed by a usual mixer.

The obtained spinning dope is spun out from an ordinary spinneret. As for the spinning method, any known wet spinning method can be applied, and the spinning method may be performed under the same conditions as those for ordinary acrylic synthetic fibers. More preferably, by performing a secondary stretching of 3 times or less with moist heat, macrovoids can be effectively imparted to the fiber, and the deodorizing performance can be improved.

The amino compound used in the present invention is a compound having an amino group in its structure.

Embedded image An aliphatic primary amine, an aromatic amine represented by R—NH ₂ (R is an alkyl group or an aryl group) and a general formula

A diamine compound represented by R- (NH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

An amide compound represented by R-CONH ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image A diamide compound represented by R- (CONH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

A hydrazide compound represented by R-CONHNH ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

A dihydrazide compound represented by R- (CONHNH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image A trihydrazide compound represented by R- (CONHNH ₂ ) ₂ (R is an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group or an aryl group) and a general formula

Embedded image H ₂ N— (CH ₂ —CH ₂ —NH) _n —H (where n is an integer of 1 or more) or

Embedded image And hydrazine, alkylhydrazine derivatives, hydrazine salts and the like. As aliphatic primary amines, decylamine, undecylamine, tridecylamine, cetylamine, etc .; as aromatic amines, benzylamine, naphthylamine, etc .; as diamine compounds,
As aliphatic diamines such as ethylenediamine, hexamethylenediamine and octamethylenediamine, aromatic diamines such as phenylenediamine, and amide compounds represented by the general formula H ₂ N (CH ₂ ) _n NH ₂ (where n is an integer of 2 or more) Are lauric amide, azelainamide, sebacin monoamide, etc., as diamide compounds, adipic amide, sebacin diamide, azelaic diamide, etc., as hydrazide compounds, benzhydrazide, acetohydrazide, etc., and as dihydrazide compounds, carbodihydrazide, Adipic acid dihydrazide, sepasic acid dihydrazide, dodecane diacid dihydrazide, isophthalic acid hydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide and the like; and alkylene imines such as diethylene triamine, trie Rentetoramin, tetraethylene pentamine, pentaethylene hexamine and the like, polyalkylene imines such as polyethylene imine, polypropylene imine, poly (2-ethyl-aziridinyl Din) and the like,
As hydrazine and alkylhydrazine derivatives, hydrazine salts such as hydrazine hydrate, monomethylhydrazine, dimethylhydrazine, tert-butylhydrazine salts, benzophenone hydrazone, acetone thiosemicarbazone, semicarbazide hydrochloride, polyhydrazine hydrazine, trihydrazide citrate, etc. Examples thereof include, but are not limited to, hydrazine sulfate, hydrazine carbonate, hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine phosphate, hydrazine bromate, and thiosemicarbazide hydrochloride.

The content of the amino compound used in the present invention is 0.1 to 10% by weight based on the acrylic synthetic fiber.
Preferably it is 0.5 to 7% by weight. Although it depends on the type of amino compound, if the content is less than 0.1% by weight, sufficient deodorizing performance cannot be provided, and if it exceeds 10% by weight, fiber quality and spinnability deteriorate, which is not preferable.

As a method of applying an amino compound to a knitted fabric, a spinning solution is spun from a die by wet spinning, and a fiber obtained by primary drawing is washed with water, dried and densified, and processed using the obtained fiber. There is a method in which the knitted fabric thus obtained is immersed in a solution of an amino compound, sprayed with the solution of the amino compound, and dried and preferably heat-treated. In the knitted fabric of the present invention, since a deodorant acrylic synthetic fiber having macrovoids and high water absorption is used, the method by immersion can be performed in a short time, and the amount of adhesion is adjusted by the amino compound in the liquid. It is carried out at a concentration and a dehydration rate, and is dried, preferably subjected to a heat treatment. In the method by spraying, the processed knitted fabric is placed on a conveyor or the like, and a certain amount of the amino compound solution is sprayed from above and / or below and dried, preferably heat-treated.

Addition of titanium oxide, a flame retardant, a light stabilizer, a heat storage agent, a pigment, a polymer used for the purpose of improving shrinkage, etc., which are usually used within the range not impairing the characteristics of the present invention, Gel tow processing and oil application for the purpose of imparting flammability and the like are optional. In addition, an additive may be used when producing a fine powder containing a metal silicate or aluminosilicate as an active ingredient within a range that does not impair the characteristics of the present invention, and may be added for improving the dispersibility of the fine powder. The use of objects is optional.

The knitted fabric according to the present invention is a knitted fabric processed using a deodorant acrylic synthetic fiber containing a polymer (B) and a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient. The method may be performed by using a generally used processing method except that the amino compound is attached to the surface in an amount of 0.1 to 20% by weight. Processing such as dyeing and printing can also be performed. Also, the mechanical properties of the knitted fabric,
For example, strength, area, air permeability, heat resistance, chemical resistance, and the like differ depending on the application to be used. Therefore, the material, thickness, structure, and the like should be appropriately selected and are not particularly limited. Although the knitted fabric of the present invention may use only the deodorant acrylic synthetic fiber of the present invention, synthetic fibers such as polyethylene, polypropylene, polyester, polyurethane, nylon, acrylic, vinylon, and aramid, acetate, rayon, cupra The fibers may be mixed with natural fibers such as regenerated fibers such as cotton, wool, and hemp, carbon fibers, glass fibers, and the like, processed into a knitted fabric, and then provided with an amino compound. The mixing ratio of the deodorant acrylic synthetic fiber containing the fine powder containing the metal silicate or the metal aluminosilicate of the present invention as an active ingredient and other fibers is not particularly limited. When importance is placed on functions, for example, flame retardancy, heat retention, moisture absorption, etc., about 5% to 50%, more preferably 5% to 30%
The knitted fabric obtained can have sufficient deodorizing performance.

[0029]

Next, the present invention will be described in detail with reference to examples. Parts and% in Examples are "parts by weight" and "% by weight" unless otherwise specified. [Deodorant] Evaluation of the deodorant performance of textile products is based on the basic smell of daily life, such as ammonia smell, which is a basic smell (rot odor of meat, components of tobacco smoke, decomposition products of sweat and urine, etc.) , Trimethylamine odor (fish rot odor, etc.), mercaptan odor (vegetable rot odor, etc.), acetic acid odor (body odor due to decomposition of sweat component, tobacco smoke component, etc.), acetaldehyde (tobacco smoke component) Etc.) were performed by the following method.

1. Trimethylamine (hereinafter referred to as TMA) removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, TMA was sealed so as to have a concentration of 10 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube. 10 pp of TMA in empty Tedlar bag as control
m and then left for 1 hour, the gas concentration was measured with a detector tube, and the TMA removal rate was calculated from the decrease rate of the concentration.

2. Ammonia removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, ammonia was sealed to a concentration of 40 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube. Add 4 ammonia to empty Tedlar bag as control
After sealing the mixture to a concentration of 0 ppm and leaving it to stand for 1 hour, the gas concentration was measured with a detector tube, and the removal rate of ammonia was calculated from the decrease rate of the concentration.

3. Ethyl mercaptan (hereinafter referred to as EMP) removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, EMP was sealed so as to have a concentration of 20 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube. 20 pp of EMP in empty Tedlar bag as control
m and then left for 1 hour, the gas concentration was measured with a detector tube, and the EMP removal rate was calculated from the concentration decrease rate.

4. Acetic acid removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, acetic acid was sealed so as to have a concentration of 20 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube.
As a control, acetic acid was sealed in an empty Tedlar bag so as to have a concentration of 20 ppm. After leaving for 1 hour, the gas concentration was measured with a detector tube, and the acetic acid removal rate was calculated from the decrease rate of the concentration.

5. Acetaldehyde removal rate measurement method Tedlar bag (made of vinylidene fluoride film, 5 l)
Then, 3 g of a fiber sample is put in the container, and the container is sealed. Next, acetaldehyde was sealed to a concentration of 25 ppm, and the mixture was allowed to stand for 1 hour, and then the gas concentration was measured with a detector tube. As a control, acetaldehyde was sealed in an empty Tedlar bag so as to have a concentration of 25 ppm, and after allowing to stand for 1 hour, the gas concentration was measured with a detector tube, and the acetaldehyde removal rate was calculated from the decrease rate of the concentration.

[Washing resistance] The washing resistance test was conducted according to JIS L
Performed according to 1018 “Home Electric Washing Method”.

[Porosity] In the present invention, the polymer (B)
The macro voids obtained by the method described above were evaluated by the water absorption rate for convenience because the macro voids opened on the surface communicated with the internal macro voids to improve the water absorption performance, and were measured by the following method. The water absorption is a measured value of 100% of the deodorant acrylic synthetic fiber of the present invention. 0.5 g of cotton is immersed in pure water for 5 minutes and then treated with a centrifuge for 2 minutes to remove water between fibers, measure the weight (W0), and further dry the cotton to dry weight (W1) was measured, and the water absorption was calculated by the following equation. Water absorption (%) = (W0−W1) / W1 × 100 *

Examples 1 to 5 and Comparative Examples 1 to 5 The production of an acrylonitrile copolymer was carried out by using acrylonitrile (hereinafter referred to as AN) / methyl acrylate / 2-acrylamide-2-methylpropanesulfonic acid sodium (hereinafter referred to as SAM). ) = 91.2 / 8.0 / 0.8 is polymerized in dimethylformamide (hereinafter referred to as DMF) using azobisisobutyronitrile as an initiator to remove residual monomers. Do
Thereafter, the copolymer concentration was adjusted to 20 to 30%.

The polymer (B) was prepared using acetyl cellulose, which is a cellulose derivative, so as to have a DMF content of 20 to 30%.

In the fine powder, the composition ratio of the metal aluminosilicate as an active ingredient is SiO ₂ : 58 mol%, Al ₂ O
₃ : 7 mol%, ZnO: 35 mol%, an average particle diameter of 3.5 μm, and a specific surface area of 200 m ² / g were used, and the DMF was adjusted to 20 to 25%.

The amino compound was prepared using adipic dihydrazide in distilled water so as to be 1 to 20%.

The DMF solution of acetyl cellulose obtained and the dispersion of the fine powder were added to the acrylonitrile copolymer at the addition rates shown in Table 1 and mixed to obtain a spinning stock solution.

The spinning stock solution was spun into a 58% aqueous solution of DMF at 22 ° C., subjected to primary stretching six times in three steps while removing the solvent, and then washed with water at 60 ° C. to remove DMF.
After that, the fibers in the gel swelling state are immersed in the amino compound solution, and then dried at 130 ° C. with a heater roller under tension, and subjected to a second stretching 1.2 times under moist heat at 100 ° C., and after crimping. Perform a wet heat treatment at 105 ° C.
It was cut to 51 mm. Using this fiber, ordinary cotton spinning was performed to obtain a spun yarn having a count of 40/1. Then the diameter 11
Using a 22-inch circular knitting machine, a green fabric of the milling structure was made, and the knitting was performed sequentially by refining, bleaching, drying, finishing, and setting.

In Comparative Examples 1 to 5, the polymers (B), fine powders and amino compounds used in Examples 1 to 5 were added and added to the acrylonitrile copolymer in ratios out of the range. Each step and each evaluation were performed in the same manner as in Examples 1 to 5.

Table 1 summarizes the above results.

[0045]

[Table 1]

As is clear from Table 1, it can be seen that the product of the example has superior deodorizing performance as compared with the product of the comparative example.
In the case of Comparative Examples 1 and 2 in which the addition ratio of the copolymer (B) and the fine powder to the acrylonitrile-based polymer was increased outside the range, the filtration pressure increased during spinning, and yarn breakage occurred, making spinning impossible. Was. In the case where the addition ratio of the fine powder was reduced outside the range as in Comparative Example 3, the spinning operability and the fiber quality were good, the water absorption was high, and macrovoids were formed. Was not obtained. In Comparative Example 4 in which the content of the amino compound was reduced outside the range, the deodorizing performance against acetaldehyde was insufficient, and satisfactory performance was not satisfied. In Comparative Example 5 in which the content of the amino compound was out of the range, the deodorizing performance was good, but the texture of the fiber was lowered and the product could not have sufficient quality.

Examples 6-8, Comparative Examples 6-7 The deodorant acrylic synthetic fiber used in Comparative Example 4 was 38 mm.
After the fixed length cut, it was immersed in an amino compound solution so as to obtain the adhesion amount shown in Table 2, dehydrated, heat-treated at 100 ° C, and knitted in the same manner as in Examples 1 to 5.
Incidentally, isophthalic hydrazide was used as the amino compound. Table 2 shows the evaluation of deodorant performance and texture of the obtained knitted fabric. In addition, in Comparative Examples 6 and 7, the amount of adhesion was out of the range.
The same was done.

[0048]

[Table 2]

As is clear from Table 2, those without the amino compound shown in Comparative Example 6 were insufficient in deodorizing performance against acetaldehyde and could not satisfy satisfactory performance. Further, in Comparative Example 7 in which the amount of amino compound attached was out of the range, the deodorizing performance was good, but the fiber texture was lowered and the quality was not sufficient, and the processability into a knitted fabric was not sufficient. Did not.

Examples 9 to 12 After the fiber (C) used in Examples 1 to 8 was cut at a constant length of 76 mm, a card sliver was obtained through a carding machine. On the other hand, 650,000 denier of ordinary acrylic fiber (D) (Kanebo acryl XQ3) was passed through a tow reactor at 3 denier to obtain a tous sliver having a sliver shrinkage of 22%.
Further, after mixing the acrylic fibers (C) and (D) with a drawing machine at the blending ratios shown in Table 3, ordinary worsted spinning was carried out to obtain 2 /
The 28th spun yarn was obtained. Next, the above spun yarn is used for the pile ground, and the polyester filament 15 is used for the insertion yarn and the chain yarn.
Using 0d / 48f and 200d / 48f, a 16-gauge, 26 mm kettle width double Russell machine was used to apply Mayer blanket cloth (4000 inserted yarns, 4000 chain yarns, 1000 pile yarns, 140 cm width, 550 g / m ² ). Obtained.
Next, screen printing was performed on the front of the blanket, and continuous plain dyeing was performed on the back of the blanket, and heat treatment was performed at 98 ° C. for 20 minutes using a continuous steaming machine. Further, successive washing with water, softening, drying, hair removal (dual breaker, 4 m / min, 4 passes), polisher (electro polisher, 8 m / min, 2 passes of 170 ° C. and 150 ° C.), shearing (shearing) Machine, 8m /
Min, 2 passes), cutting and sewing to obtain a Meyer blanket. As is evident from Table 3, the products of Examples had excellent deodorizing effect, durability, texture and quality of knitted fabric even when used by mixing with other fibers.

[0051]

[Table 3]

Examples 13 to 15 and Comparative Examples 8 to 10 An acrylonitrile copolymer consisting of AN / vinylidene chloride / SAM = 57/40/3 was polymerized in DMF using azobisisovaleronitrile as an initiator. The remaining monomer is removed, and then the copolymer concentration is reduced to 20 to 30.
%.

The polymer (B) was prepared using polyvinyl butyral so as to have a DMF content of 20 to 30%.

The fine powder used was the same as in Examples 1 to 5, and was adjusted to 15 to 20% in DMF.

The obtained DMF solution of polyvinyl butyral and the dispersion of the fine powder were added to the acrylonitrile copolymer at the addition ratio shown in Table 4 and mixed to obtain a spinning stock solution.

The spinning solution was spun into a 57% aqueous solution of DMF at 18 ° C., stretched 5.9 times in three steps while removing the solvent, and then washed with water at 60 ° C. to remove DMF. After that, the fiber in the gel swelling state is dried at 130 ° C. by a heater roller under tension, the secondary stretching is performed at 1.2 times under the moist heat of 100 ° C., and after the crimp is applied, the moist heat treatment is performed at 105 ° C. , 51 mm.

The knitted fabric prepared in the same manner as in Examples 1 to 5 using the obtained fibers was impregnated with an aqueous solution of an amino compound by padding, and squeezed with a mangle roller so as to obtain the adhesion amount shown in Table 4. The knitted fabric was tenter dried at 100 ° C. for 2 minutes, and then baked at 150 ° C. for 1 minute.
In addition, polyethyleneimine (SP-003 manufactured by Nippon Shokubai Kagaku Co., Ltd.) was used as the amino compound. Comparative Examples 8 to 10
Is the one in which the amount of the amino compound used in Examples 12 to 14 was out of the range on the knitted fabric, and each step and each evaluation were performed in the same manner as Examples 12 to 14.

Table 4 summarizes the above results.

[0059]

[Table 4]

As is evident from Table 4, it can be seen that the product of the example has superior deodorizing performance as compared with the product of the comparative example.
In the case of Comparative Example 8 in which the addition ratio of the fine powder was reduced outside the range, spinning operability and fiber quality were good, the water absorption was high, and macrovoids were formed. Therefore, the deodorizing performance was insufficient, and satisfactory performance could not be satisfied. In Comparative Example 9 in which the amount of amino compound attached was reduced outside the range, the deodorizing performance against acetaldehyde was insufficient, and satisfactory performance was not satisfied. In Comparative Example 10 in which the addition rate of the polymer (B) was reduced outside the range, the addition amount of the fine powder and the adhesion amount of the amino compound were within the range, but the addition rate of the copolymer (B) was less than the range. For this reason, formation of macrovoids was insufficient, and sufficient deodorizing performance could not be obtained. In contrast,
In the examples, satisfactory results were obtained in deodorizing performance, durability, texture and quality of the knitted fabric.

Examples 16 to 19 After the deodorant acrylic synthetic fiber (E) used in Examples 11 to 13 was cut at a fixed length of 38 mm, ordinary 1.5 denier acrylic fiber (Kanebo acrylic XQ3) (D )
Was mixed at the ratios shown in Table 57, and then ordinary cotton spinning was performed to obtain a spun yarn of 40th count. A plain woven fabric was formed from the spun yarn at a density of 126 warp / inch and 80 wefts / inch. Table 5 shows the evaluation of the deodorant performance and the antibacterial performance of the obtained plain fabric. As is clear from Table 5, the product of the example had an excellent deodorizing effect.

[0062]

[Table 5]

[0063]

The deodorant knitted fabric of the present invention is obtained by mixing a conventionally used acrylonitrile copolymer (A) with a polymer which is miscible with the copolymer (A) and is incompatible with the copolymer (A). (B) and a fine powder containing metal silicate or metal aluminosilicate as an active ingredient, which is a deodorant knitted fabric obtained by adhering an amino compound to a knitted fabric made of an acrylic fiber. And a good deodorizing performance with washing resistance without lowering the fiber performance and the texture, color and strength of the knitted fabric when using acrylic fibers. The knitted fabric obtained by the present invention is used only with the deodorant acrylic synthetic fiber of the present invention, and under the same process and conditions as ordinary acrylic synthetic fiber, with other fibers such as polyester, nylon, wool, and cotton. Deodorizing knitted fabrics that can be mixed woven and knitted fabrics and are inexpensive for clothing, interior, and industrial materials that require deodorizing performance, and have excellent deodorizing performance and washing resistance And a method for producing the same, which is extremely industrially significant.

Claims (2)

[Claims] 1. A copolymer (A) containing acrylonitrile as a main constituent unit, and a polymer (B) miscible and incompatible with the copolymer (A) in an amount of 1 to 20% by weight. In the acrylic synthetic fiber, the polymer (B) is present in a phase-separated state, and a fine powder containing an active ingredient of a metal silicate or aluminosilicate having an average particle size of 0.5 to 10 μm is used as a powder. A knitted fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight, and having an amino compound attached thereto in an amount of 0.1 to 20% by weight. Knitted fabric. 2. A copolymer (A) containing acrylonitrile as a main constituent unit and 1 to 20% by weight of a polymer (B) miscible and incompatible with the copolymer (A). In the acrylic synthetic fiber, the polymer (B) is present in a phase-separated state, and a fine powder containing an active ingredient of a metal silicate or aluminosilicate having an average particle size of 0.5 to 10 μm is used as a powder. 0.1 to 20% by weight of an amino compound is applied to a knitted fabric processed using a deodorant acrylic synthetic fiber containing 0.5 to 20% by weight by immersion or spraying. A method for producing a deodorant knitted fabric.